Epoxy ether polyamides



Unite States 3,042,692 Patented July 3, 1962 This invention relates tonew compositions of matter and more particularly to polyamides ofepoxidized fatty materials. These compounds may be exemplified by thefollowing formula for the diamide:

OH HO epoxidizing unsaturated fatty polyamides or by the selectiveaminolysis of an ester of the epoxy-containing material with apolyamine. Bis (epoxy stearamido) ethane, for example, may be preparedin the former method by the epoxidation of dioleoyl ethylenediamine,while production of the same compound by the latter method is bestillustrated by the reaction between methyl epoxystearate andethyleuediamine.

The epoxidation reaction may be carried out by one of the knownepoxidation procedures employing one of the per acids such as performicacid, percetic acid, or perphthalic acid. The selective aminolysisreaction is surprising in that the reaction takes place between theamino group of the polyamine and the carbonyl group of the epoxy esterwhile the epoxidized 'configiration is left undisturbed.

The epoxy aliphatic acids and esters included Within the scope of thisinvention are those acids and esters containing from 10 to 22 carbonatoms in the acyl portion of the molecule. These acids may be derivedfrom naturallyoccurring fatty materials having a substantial portion ofunsaturated acids, i.e., monoethenoid, d-iethenoid, and triethenoid. Theunsaturated acids of most common occurrence in fatty glycerides are:oleic, (cis A9,10 octadecenoic), palmitoleic (A9,10-hexadecenoic),linole'ic (cis A9,l0-cis 1312,13 octadecadienoic), linolenic (139,10,12,13, 15,16-octadecatrienoic), and ricinoleic (12-hydroxy-A9, l0octadecenoic) acids.

Other fatty acids of less common occurrence include A9,10- andA4,5-decenoic acid; A3,4-, A4,5-, and A9,10- dodecenoic acid;9,10-tetradecenoic acid (myristoleic acid), and A4,5- andA5,6-tetradecenoic acid; cis A6,7- octadecenoic acid (petroselenicacid); A11,12-octadecenoic acid (vaccenic acid); A9,l0-eicosenoic acid(gadoleic acid); A1l,12-eicosenoic acid;A6,7,10,1l,14,l5-hexadecatrienoic acid; and cis A13,l4-docosenoic acid(erucic acid). Also included are unsaturated materials such asundecylenic and acetyl ricinoleic acids.

Amines which may be used in the preparation of the novel compositions ofthis invention include polyamines generally, such as di-, triandtetrarnines. Specific examples of these compositions areethylenediamine, tetramethylenediamine, pentamethylenediamine,diethylenetriamine, triethylenetetramine, and substituted diamines suchas 2,4 diamino-Z-methylpentane as well as aromatic diamines such asphenylene diamine. While in the examples which follow ethylenediarnineis the preferred polyamine employed in forming bis (acylamido) alkane,

it should be understood that triamines will form the cor-' 2 respondingtri's-amido-compound, while a tetramine produces a tetrakisconfiguration.

The following examples, which illustrate methods of preparingcompositions representative of this invention, are to be considered. inno way limitative, the scope of the invention being defined by theappended claims.v

EXAMPLE I Bis (Epoxystearamido) Ethane 58.5 gramsdioleoylethylenediamine (prepared by the reaction between an excessofoleoyl chloride and ethylenediamine in pyridine and purification of theresulting product) is dissolved in 200 ml. benzene. The mixture isstirred and 50 ml. of 40% peracetic acid is added to the benzenesolution. After 2 hours stirring and holding the temperature at about 50C., a solid material starts to form, and an additional ml. .of benzeneis added. After an additional 2 hours stirring, the reaction is stopped,and the benzene solution is washed with water, dilute sodium bicarbonatesolution, and again with water. The benzene is evaporated on the steambath, leaving a porous solid cake. The last traces of benzene areremoved from this porous cake by means of vacuum. The light coloredsolid product has an oxirane oxygen content of 4.9%. Theoretical oxiraneoxygen content=5.18%.

EXAMPLE II Bis (Epoxystearamido) Ethane by Selective Amidation A mixtureof 5. grams freshly distilled ethylenediamine and 60 gramsmethylepoxystearate (oxirane oxygen =4.9%) is stirred continuously for24 hours, while the temperature is maintained at about 100. C. At theend of this time, the reaction mixture is cooled, and the resultingproduct is washed. with diethyl ether to' remove unreacted methylesters. The solid bis (epoxystearamido) ethane remaining after removalof all traces of ether contains 4.7% oxirane oxygen.

EXAMPLE III Bis(undecanoamido) benzene is prepared by reacting 1 mole ofphenylene diamine with 2.2 moles undecylenic acid chloride in pyridinesolution. The product is purified by washing with 5% sodium hydroxidesolutionand also with water. This diamide is dissolved in about 5volumes of benzene and then epoxidized by the addition of 2.5 moles (500ml. of 40%) peracetic acid. The procedure involves stirring the benzenesolution of the diamide vigorously while the peracetic acid is'added tothe solution. The temperature is maintained at about 60 C. during theaddition of the peracetic acid and for 6 hours more. The reactionmixture is then cooled and the henzene solution is washed with warmwater, dilute sodium bicarbonate, and again with water. Removal of thebenzene yields a light colored solid, which is principally bis(epoxyundecanoamido) benzene having an oxirane oxygen content of 5.1%

The epoxy polyarnides disclosed and claimed'herein are valuablecompositions inasmuch as they form insoluble infusible cross-linkedpolyether polyamide resins. These resins find use in tooling andstructural materials and in electrical components and wire coatings.

wherein A is an aliphatic or aromatic group having a valence s. s =2-8and is the number of fatty chains per molecule. x=13 and is the numberof epoxy groups per fatty chain. m and p are numbers from -15. n is 2 ormore and m+3x+p+1=10-22.

Another method of preparingt-hecross-linked polyamide is by way ofamidation of the polyether epoxy.

fatty acid or ester. In this modification of the cross-linkingprocedure, the oxirane configuration is broken prior to the amidation ofthe'ester groups of the epoxy-con- EXAMPLE VI The purified methyl estersof polyether fattyacids (15 grams) and 1.5 grams of ethylenediamine aremixed, and the mixture is stirred. The liquid reactants are not miscibleat room temperature, but dissolve on Warming. The mixture is heateduntil the temperature reaches 200 C. At about 160 C. some evolution ofmethanol is apparent. Heating at 200 C. is continued for about 10minutes, and the mixture is then cooled. A tough, flexible solid, whichis insoluble in organic solvents, is obtained. The solid product issomewhat soluble in alcoholic KOH after prolonged boiling.

Obviously, many modifications and variations of the invention ashereinbefore set'forth may be made without departing from the spirit andscope thereof, and, therefore, only such limitations should be imposedas are indicated in the appended claims.

Prepared in accordance with the method set forth in copendingapplication Serial No. 651,822 filed April 10, 1957.

I claim: 1

1. A polyether polyamide of 10-22 carbon fatty acids in which the acylgroups of said fatty acids are crosslinked through ether groups locatedon contiguous carbons of the fatty acid chains.

' 2. A polyether polyamide in accordance with claim 1 wherein thepolyamide is a 'diamide' 1 I 3. A polyether polyamidein accordance withclaim 1 wherein the polyamide is a triamide.

4. A polyether polyamide in accordance with claim 1 wherein thepolyamide is a tetramide.

5. A process for preparing cross-linked polyether polyamides ofoxirane-containing 1022 carbon fatty acids contiguously substitutedethergroups.

6. A process for preparing cross-linked polyether polyamides ofoxirane-containing 10-22 carbon fatty acids taining material. By thismethod, methyl epoxystearate may be treated with a'polymerizationcatalyst to form a 'polyethenwhich may then be amidated with the desiredlpolyami'ne.

- The following examples'show the aforementioned methods.of producingthe place. As the ether boils ofi as a result of the heat generated, theremaining foam solidifies to give a flexible, tough solid. V a l diethylether, 'and an immediateexothermic reaction takes comprising: heatingand reacting said polyamide with boron trifluoride to break the oxiraneconfiguration and cross-link the fatty chains of said fatty acidsthrough contiguously substituted ether groups.

7. The process of claim 6 wherein the polyamide is his-(epoxystearamido) ethane.

References Cited in the file of this patent 'UNITED STATES PATEIWTS2,450,940 Cowan et a1. Oct. 12, 1948 2,555,111 Bradley May 29, 1951"2,673,861 Weisblat et al. Mar. 30, 1954 2,682,547 Clemens et al. June29, 1954 2,730,531 Payneet al. Jan. 10, 1956 2,743,285 Wilkes et a1 Apr.24, 1956 2,745,846 Dazzi May 15, 1956

1. A POLYETHEER POLYAMIDE OF 10-22 CARBON FATTY ACIDS IN WHICH THE ACYLGROUPS OF SAID FATTY ACIDS ARE CROSSLINKED THROUGH ETHER GROUPS LOCATEDON CONTIGUOUS CARBONS OF THE FATTY ACID CHAINS.